Dustry in basle



Patented Nov. 25, 1930 uNiT e STATES PATENTOFFICE HANS GUBLER ANDGUILLAUME DE MONTMOLLIN, OF BASEL, AND JOSEPH SPIELER, 0F LAUFEN,SWITZERLAND, ASSIGNORS TO THE FIR-M SOCIETY OF CHEMICAL IN DUSTRY INBASLE, OF BASEL, SVJIT ZEBLAND DYESTUFFS CONTAINING METALS AND PROCESSOF MAKING SAME No Drawing. I Application filed July 9, 1929, Serial No.377,068, and in Switzerland July 14,1928.

The present invention relates to new dyestuffs containing metals. Itcomprises the new products, the method of producing same in substance,in the dye-bath, or on the fiber,

the application thereof and the material which has been dyed with thenew products. It has been found that the new dyestuffs containingcomplex bound metals which correspond to azo-dyestuffs of the general informula I OH wherein :1: stands for an organic residue containing atleast one carbon atom, the

groups being linked to such carbon atoms of p said residue which areunited by a double flu bond with a nitrogen, oxygen or sulfur atom,

and wherein R means the residue of a ben- Zene nucleus characterized bythe presence of a COOK-group (R=H or alkyl) standing in 30ortho-position to the -N=N- group, and

R isthe residue of a benzene nucleus characterized by the presence of, a(DOOR-o1- OR group (R=Hor allryl) standing in ortho- H position to'theVN=N group, are Very valuable cotton dyestuffs which yleld on the theresidue of the anthranilic acid or of an ortho-am1nophenol, and w forthe residues (y being any monovalent radical) The anthranilic acid can,however, be replaced by its esters, the ortho-aminophenols by theiralkyl-ethers, and the phosgene or triazine residues by quinazolines andpyridazines halogenated in the heterocyclic nucleus,trichloropyrimidines, dichloromethylpyrimidines and the like. i

As metals which are capable of forming complex compounds come first ofall into question: chromium, manganese, iron, cobalt, nickel, copper,etc.

These dyestuffs are most conveniently obtained by combining intermediateproducts of the general formula O H H in which 56 has the same meaningas above stated, with diam-compounds corresponding to the residues R andR The products thus obtained are then treated with agents yieldingcopper, chromium, manganese, etc., which operation may be performed insubstance, in the dye-bath or on the fiber.

' Similar products are obtained by combining 2 molecular proportions ofthe azo-dve- StUfi-Qf the general formula U Hogs- -NH2 I on in which R,has the same meaning as above stated, or 1 molecular proportion of anazodyestutl of the 'eneral formula I OH in which R has thesame meaningas above stated, and 1 molecular proportion of the aZo-dyestull oi thegeneral formula i on HOaS

Example 1 13? parts of 1-amino-2-benzenecarboxylic acid are dissolved in1000 parts of water and 120 parts of hydrochloric acid of 30 per cent.strength, the solution is cooled with ice to 5 C. and then diazotizedwith 69 parts of sodium nitrite. The diaZo-solution is run into asolution of 252 parts of the urea of 2amino- 5 hydroxynaphthalene 7sulfonic acid in 2500 parts of water and 250 parts of calcined sodiumcarbonate. The coupling is finished in a short time. The dyestutl' isisolated in the usual manner. When dry it is a brown powder whichdissolves in water to an orange solution. It dyes cotton brown-orangetints, which by after-treatment with copper salt change towards,'GllOV-." i iOl'CiPilUZ-I, with ehrw miuni or manganese salts slightlytowards red and with iron, nickel or cobalt salts towards brown.

If it is desired to convert the dyestulii in substance into a metalcompound, it is ad vantageous not to isolate the dyestutl but after thecoupling operation to heat to (3., acidity with dilute sulfuric acid andadd 300 parts of crystallized copper sulfate dissolved in 5 times itsweight of water; the whole is then stirred for 23 hours at 90 (l. Theseparated dyestulf acid of the copper Compound is treated with diluteammonia at 60 (1, and the product salted out and isolated.

The new dyestutl dyes cotton red-brown tints of remarkable fastness tolight.

The corresponding dyestutls from thio-u ea of the2-aminohydroxynaphthalene-T-sultonic acid have similar properties.

Example 2 53 parts 01 the urea of 2-amino-5-hydroxynaphtha.lene-7-sulfonic acid are coupled in the presence of sodiumcarbonate with 30.2 parts of 1-aminobenzene-2-carboxylicacidn'iethyl-ester, which has been diazotized in the usual manner. TheaZo-dyestuii thus formed precipitates and is filtered. is stirred inwater at 70 C. and there is added. an amnioniaca]. solution 01" coppersulfate. After stirring; for a short time at 70 0., the copper compoundot the azo-dyestuii' is "formed. :l t is filtered and dried.

The new dyestulli' dyes cotton tast redbrown tints of remarkabletastness to light.

A similar product is obtained when one molecular proportion of thediazorompouud oi Ii -31!)ill )i101 Z0}I ,\2-(ftl'i)()f(]li( acid methylester is coupled with 2-ainino-S-hydroxynaphthalene-T-sulfonic acid andthe dyestuii is treated with phosgrene and then with a copper salt, orfirst with a copper salt and then with phosgene.

Eula m p16 5 09 parts of l-amino-2-benzenecarboxy ic acid are dissolvedin 500 parts of water and (30 parts 0t hydrochloric acid of 30 per cent.

strength. The solution is cooled to 5 C. by means oi ice and diazot'izedby means 01 ll-.5

parts of sodium nitrite. The clear diazosolution is allowed to run intoa solution o? parts of the urea of 2-amino-S-hydrm. naphthaleno!sulfonicacid in 2500 pa water. There are then added p term of a solution oil 20per cent. strength. the whole being stirred for 2 hours at S0 -85 C. Theseparated dyestuil' acid of the copper compound is tilt cred, stirredwith dilute ammonia at 60 (1, the ammonium salt is salted out withcommon salt and filtered. The dyestutl' dyes cotton llordeaux red tintsof most excellent fastn ss to light.

Ewamp Zc 641.8 parts of the tertiary condensation product from 2molecular proportions of 2 amino-a-hydrorlynapht-halene 7 sultonic acid,1 molecuh 3 proportion of aniline and 1 molecular Pl'OPOllJlOH ofcyanuric chlorir d ssolved in 900 parts of water with addition oi 50parts of calcied sodium carbonate and there is added at 0 5 C. thediazo-sohition cotton, which are obtainable by means of a small numberof metalliferous dyestuffs which can be made in accordance with thisinvention zene nucleus characterized by the presence of a COOK-group(R=H or alkyl) standing in ortho-position to the -N=N group, and R isthe residue of a benzene nucleus characterized by the presence of aOOOR- or OR- group (R=H or alkyl) standing in ortho-position to the N==Ngroup, and, on the other hand, contain complex bound metals of theatomic weight ranging between 52.1 and 63.6, which products are darkpowders which dye vegetable fibers and artificial fibers of theregenerated cellulose orange, red, Bordeaux and brown tints of excellentfastness to light.

2. As new articles of manufacture the azodyestuffs containing complexbound metals, which, on the one hand, correspond to azo- Dvestulfcontain 1st component: corresponding with 2nd component. (diazotizingcompo- CO p mg component mg copper dyes N N H nent of the residue R2)cotton direct l-aminobenzene-5-chloro-2-carboxylic1-aminobenzene-5ch1oro-2-carboxylic Urea of 2-amino-5-hydroxynaphtha-Red brown NHL acid lene-7-sullonic acid1-aminobcnzene-5-nitro-2-carboxylic 1 -arr 1inobenzene- 5 -nitro 2-carboxylic Do. Brown acid 510 i'aminobenzene -5 methoxy 2 cari-arninohcnzene -5methoxy2-carbox- Do. Red brown boxylio acid ylie acid ILaminohenzene-2-carboxylic acid l-axnnobenzcne-achloro-2'carboxy1ie D0.Red brown aci l-hydiroxy-waminobenzene-4 sulfonic D0. Bordeaux acil-hydroxy-Z-aminobenZene-tsul amide Do. Bordeaux 1l-hydroxy-2-amino-4-nitrobenzene Do. Bordeaux D0, 1-hydroxy-2-am1no-4:fi-dinitrobengene Do. Bordeaux 1-l1ydroxy-2-aminoi-methyl-fi-nitro- Do.Yellow-brown benzene DO, 1-hydroxy-2-aminobenZene-4-sulfo-6-. D0. Red

carboxylic acid D0 1-amino-2-hydroxy-naphthalene-4su1- Do. Brown redionic acid 7 D0. Nitrated diam-compound of l-ainino- Do. Brown red 2liydroxynaphthalene 4 sulionic acid l-hydroxy-2amino-4-chlorobenzenc Do..Bordeaux l-aminobenzene-tsul[0-2 carboxylicl-arnnobenzene-4-sulfo-2-carboxy1ic Do. Brown ,i wl-aiiiiino-2-benzene-carboxylic acid i-aminobenzene-2-sulionic acid Do.Brown Do. i-ai tdno-amethoxy-benzene-a-sulfomc Do. Br wn u aei1-aminobenzene-2-carboxylie acid 1-aminol)enZene-2carb0Xyli0 acidTertiary condensation product of 2 Red brown molecular proportions of2amino-5- hydroxy-naphthalene-7-sulIonic acid, 1 molecular proportion ofaniline and 1 molecular proportion of cyanuricchloride Wh t We l i idyestuffs of the general formula 1. As new articles of manufacture theazodyestuffs containing complex bound metals, nms- -N-x-N '-so3n which,on the one hand correspond to azo- H H N N R dyestuffs of the generalformula l OH OH noas 03H H wherem 2? stands for an. organlc residue con--N=N-R taining at least one carbon atom, the

wherein c0 stands for an organic residue containing at least one carbonatom, the

groups being linked to such carbon atoms of said residue which areunitedby a double bond with a nitrogen, oxygen or sulfur atom, and wherein Rmeans the residue of a bengroups being linked to such carbon'atoms ofsaid residue which areunited by a double is the residue of a benzenenucleus churucterized by the presence of a COGR- or OR- group (R=II oralkyl) standing in orthoposition to the ll ilgroup, and, on the otherhand, contain complex bound metals of the atomic weight ranging between56 and 63.6, which produc s are durk powders which dye vegetable hersand artificial fibers 01': the regenerated cellulose orange, red,Bordeaux, and brown tints of excellent test ncss to light.

3. As ne articles of manufacture the 2120- dycst-uli's containingcomplex bound copper, which correspond to the nZo-dyestuiii's ot thegeneral formula -N-IN l on on wherein 0; stands for an organic residuecontaining at least one carbon atom, the

MN I l groups being linked to such carbon atoms of said residue whichare united by at double bond with a nitrogen, oxygen or sulfur atom, andwnerein R means the residue of :1 benzene nucleus characterized by thepresence of a COOK-group (3 H or ulkyl) standing in ortho-position tothe l\ N-- group, and R is the residue of n benzene nucleuschuracterized by the presence of a 6083- or Ollgroup (R H or ulkyl)standing in orthoposition to the l\ N- group, which prod.- ucts are darkpowders which dye vegetable fibers and artificial fibers of the regenrated cellulose orange, red, Borlcnux, and brown tints of excellentttestness to light.

l. As ne articles of nienuinctnre the nzodyestuii's containing complexbound copper, which correspond to the ezo dycstutis of the generalformula dyestuiiis containing complex bound copper,

which c respond lo the uzoulyesiiilis m" the wherein R, means theresidue of benzene nucleus characterized by the presence of u curboxylgroup standing in ortho-position to the -N=l\ group, and 1'3 the re idue0 1' n ben'lsene nucleus characterized by the once of n cnrboxyl orhydroxyl group is general formula inn in ortho-position t theaxe-groups" which products are dark powders which dye vouci hc n"- tublefibers and artificial fibe s an" generatedcelhuoseorunge red, l

' I i" crown ililLS or excellent t st to ligrit.

llli products dyed with the products dyed with the products

